Biobased compositions

ABSTRACT

A composition comprised of a component selected from the group consisting of a biobased bis-alkyl succinate and a biobased bis-alkyl sebacate, each derived, for example, from the esterification of biobased diacid such as succinic acid or sebacic acid, and a biobased alcohol and a biobased polyester.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.17/176,874 filed on Feb. 16, 2021, the content of which is incorporatedherein by reference in its entirety.

FIELD OF THE INVENTION

This disclosure is generally directed to compositions comprised of abiobased polyester, and a component selected from the group consistingof a biobased bis-alkyl succinate, a biobased bis-alkyl sebacate, andmixtures thereof; plasticizers comprised of biobased bis-alkylsuccinates and biobased bis-alkyl sebacates derived, for example, fromthe esterification of a biobased diacid, such as succinic acid orsebacic acid, and a biobased alcohol.

OTHER RELATED APPLICATIONS

In U.S. Pat. No. 10,934,384 issued Mar. 2, 2021, there are illustratedpolyurethane elastomers, foam compositions, and processes thereof, thedisclosure of this patent being totally incorporated herein byreference.

In copending U.S. patent application Ser. No. 17/107,381, there areillustrated a number of biocides containing polyurethane elastomers,foam compositions, and processes thereof, the disclosure of thiscopending application being totally incorporated herein by reference.

In U.S. Pat. No. 10,934,385 issued Mar. 2, 2021, there are illustratedbiocide containing polyurethane elastomers, foam compositions, andprocesses thereof, the disclosure of this patent being totallyincorporated herein by reference.

BACKGROUND

A number of plasticizers can be added to polymers to, for example,render them softer, flexible, with reduced viscosity, and decreasedglass transition temperatures. Examples of plasticizers utilized arephthalates, such as di-n-butyl phthalate, bis(2-ethylhexyl) phthalate,dioctyl phthalate, and the like, added to polymers such aspolyvinylchloride (PVC), polyesters, polycarbonates, polystyrenes,polyethylenes, polyamides, polypropylenes and synthetic rubbers. Theplastic materials of polymers and plasticizers are utilized in a widerange of applications in packaging, automotive, furniture, constructionmaterials, aerospace, clothing, apparels, and other consumer goods.These plasticizers are synthetic chemicals derived from fossil fuels,and their production contributes heavily to greenhouse gas emission andclimate change. Furthermore, phthalate plasticizers are not chemicallybound to the polymers, and when used as consumer products leach out andare exposed through direct contact or indirectly through theenvironment, and through ingestion, inhalation, or dermal exposure haveposed many adverse toxic health effects in humans. Thus, there is a needfor non-toxic plasticizers, and there is also a need for plasticizersderived primarily from a biomass such that there is less dependency onfossil fuels which accelerates climate change.

Disclosed in U.S. Pat. No. 10,633,522 are renewable resin compositionsthat include cassava starch, polybutylene, polybutyleneadipate-co-terephthalate and a non-biobased plasticizer that includesphthalate esters, and related esters, glycerol triacetate, glycerol monoand diacetates, glycerol mono, di, and tripropionates, butanoates,stearates, and acid esters such as lactic acid esters, citric acidesters, adipic acid esters, stearic acid esters, and oleic acid esters.

Illustrated in U.S. Pat. No. 10,519,296 are polyester plasticizercompositions useful as adhesives, caulk, sealants, vinyl and polymericcompositions comprising low molecular weight oligomeric dibenzoatesprepared by end-capping a polyester plasticizer, having alternatingunits of glycols or diols and dibasic acids, with benzoic acid.

In U.S. Pat. Nos. 9,289,012 and 8,973,588, there is disclosed aplasticizer composition that can be utilized for degradable polyesterfilters. A filter material adapted for use as a filter element of asmoking article is disclosed, the filter material being in the form of afibrous tow that includes a plurality of filaments of a degradablepolyester and a plasticizer composition applied thereto, the plasticizercomposition and the degradable polyester having a Relative EnergyDifference calculated using Hansen Solubility Parameters of less thanabout 1.3 degradable polyester examples include polyglycolic acid,polylactic acid, polyhydroxyalkanoates, polycaprolactone, polybutylenesuccinate adipate, and copolymers or blends thereof. Exemplaryplasticizer compositions disclosed include one or more ofdimethylisosorbide, propylene carbonate, methylbenzyl alcohol, glycerolcarbonate acetate, glycerol carbonate ethyl ether, and mixtures thereof,optionally in combination with triacetin.

Illustrated in U.S. Pat. No. 9,359,487 are plasticizers based on mixedesters of succinate for use in a thermoplastic polymer. The plasticizersaccording to the disclosure of this patent are a succinate mixed esterof benzyl on the one part and branched nonyl or decyl on the other part.

Disclosed in U.S. Pat. No. 9,550,882 are formulations for thepreparation of a wiping blade element for a vehicle windscreen wiperblade. The formulation has an elastomer material based on chloroprenerubber in which plasticizing additives are incorporated, where theplasticizing additives include octyl sebacate and naphthalic oilplasticizers. Similar plasticizers are also disclosed in U.S. Pat. Nos.6,770,372 and 6,271,294 for polymer compositions based on vinylidenefluoride resins which are particularly suitable for the manufacture ofpipes, and wherein the plasticizer includes non-biobased dibutylsebacate and non-biobased di-octyl-sebacate.

Additionally, illustrated in U.S. Pat. No. 4,085,080 are compositioncomprising a nylon resin, an additive insoluble in nylon and arelatively non-polar ester plasticizer selected from the groupconsisting of non-biobased adipate or a sebacate such as dibutylsebacate, dihexyl sebacate, dicyclohexyl sebacate, dioctyl sebacate,didodecanyl sebacate, diphenyl sebacate and diphenyl adipate.

Moreover, disclosed in U.S. Pat. No. 4,666,968 are ester plasticizersfor polyurethane compositions comprising the reaction product of anisocyanate compound and a polyol in the presence of a plasticizercompound having a solubility parameter of between about 8.3 and about8.9 or between about 9.1 and about 9.7, and wherein the plasticizersinclude ditridecyl adipate, diundecyl phthalate, diisodecyl phthalate,or dibutyl phthalate.

Certain polyurethane flexible foams (PU) are known for their uses asfootwear, automotive applications, yoga mats, mattresses, and the like.However, conventional petrochemical based materials being used tomanufacture polyurethane (PU) flexible foams usually have a negativeimpact on the environment. Thus, the increase in environmentalconsciousness has necessitated a demand for “greener” materials thatcould be partially addressed by using renewable materials in theproduction of PU foams. Therefore, an important need resides inproviding polyurethane elastomer foams with a bio-content of, forexample, from about 70 percent to about 85 percent. While increasingrenewable content, it is also desired to maintain or improve theperformance properties of the foam. Often, when introducing biobasedmaterials into foam formulations, there is a reduction in mechanicalproperties as these materials disrupt the foam network responsible forthe mechanical strength. For example, in the footwear industry,mechanical strength properties, such as tensile strength, ultimateelongation, tear strength, and resilience, can be important to a foam'sperformance. Furthermore, excessive use of plasticizers in polymers canlead to long term leaching or separation of the plasticizer from thepolymer resulting in reduction of mechanical performance and unwantedplasticizer separation from the polymer.

Polyurethane elastomers can be derived primarily from a two-componentreaction or curing of a diisocyanate component and a polyol. In idealcircumstances, both the diisocyanate and polyol are in liquid formduring the reaction at a temperature from about 25° C. to about 80° C.Polyols derived from ethylene oxide and or propylene oxide are typicallyliquid and of low viscosity under these conditions. However, thesepolyols are derived from fossil fuels. Polyols comprised of polyesterresins with hydroxyl terminated end groups may also be used forpreparing polyurethane foams, which in some instances are derived frombiomass or biobased materials such as disclosed in copending applicationSer. No. 17/015,669. These polyester polyols can be solid or viscousliquids at the temperature range of from about 25° C. to about 80° C.,and thus require the use of diluents to render them to liquid states,and similarly with some solid diisocyanates as well. Since there is adesire to utilize biobased polyester polyols, and biobased plasticizerscan be utilized as effective diluents to solubilize the polyester polyolto a liquid of low viscosity state and for providing the plasticizationof the resulting polyurethane elastomer. Ideally, the amount ofplasticizer should be added in a minimal enough quantity to solubilizethe polyester polyol, and to provide with plasticization of theresulting polyurethane elastomer. If too much plasticizer is utilized,this can result in over plasticization with undesired mechanicalperformance and leaching of the plasticizer from the polyurethane. Tooptimally add just enough plasticizer to the formulation to achieve bothsolubility and plasticization properties, it is necessary to closelymatch the solubility parameter of the plasticizer with that of thepolyester polyol and resulting polyurethane elastomer, such that theenergy difference between the solubility parameters of these componentsis equal to or less than about 3 Mpa^(1/2).

Footwear, like athletic shoes, whether for running or engaging in sportsactivities, lose massive amounts of energy due to impact and shock,especially in the midsoles. A well cushioned shoe disperses the impactand shock that, for a period, keeps the feet comfortable and preventsthe feet from hurting. High performance athletic shoes have wellcushioned midsoles that transfers the impact into forward motion orlift-offspring-like effect, as if the impact/shock is being turned intoa return energy.

There is a need for polyurethane elastomers that can be selected formolded flexible parts, footwear insoles or midsoles, and whichelastomers with, for example, a combination of specific mechanicalproperties, such as a hardness of, for example, from about 20 to about60 Asker C, from about 15 to about 60 Askar C, from about 20 to about 50Asker C, and from about 15 to about 35 Askar C, and for insoles ahardness of, for example, from about 22 Asker C to about 44 Asker C, andfor midsoles a hardness of from about 40 to about 60 Asker C, andwherein said polyurethane elastomer composition is derived from abiobased polyester, a biobased plasticizer and a diisocyanate, and otheradditives such as dyes, surfactants, crosslinkers, chain extenders anddiisocyanates, and wherein the polyurethane has a high biomass contentof over 75 percent by weight, and wherein the solubility parameter ofthe plasticizer, the polyester polyol and resulting polyurethaneelastomer have an energy difference between the solubility parameters ofthese components of less than about 3 Mpa^(1/2).

Also, there is a need for compositions and processes for flexiblepolyurethane elastomer foams with improved characteristics, and thatincludes as a component a biobased polyol polyester, which arehydrolytically stable, and comprised of biobased polyester polyols witha solubility parameter of from about 8 to about 10 Mpa^(1/2), and acomponent of a biobased plasticizer with a solubility parameter of, forexample, from about 8 to about 10 Mpa^(1/2), and wherein the differencein solubility parameter between the polyester polyol and the biobasedplasticizer is less than 5 Mpa^(1/2), less than 3 Mpa^(1/2), or lessthan 1.3 Mpa^(1/2), such that optimal compatibility is achieved. Whenthe difference in solubility parameter between the polyester polyol andplasticizer is less than 5 Mpa^(1/2), in solubility parameter betweenthe polyester polyol and plasticizer is less than 5 Mpa^(1/2), theresulting polyurethane elastomer with the other additives anddiisocyanates results with minimal required plasticizer and betteroverall mechanical performance.

Another need is the hydrolytic stability of a polyurethane elastomer.Hydrolysis can be described as the reaction between water and apolymeric material in which a definite chemical change occurs. Materialswhich do not react with water can be said to possess 100 percenthydrolytic stability. Polyurethanes can be hydrolyzed by water undercertain conditions and the chemical changes involved result in adeterioration in properties of the material. These changes can befollowed chemically or physically but under severe conditions thedegradation is readily apparent. In this case, the polyurethane canchange from being a tough elastic material to a soft plastic substancewith little or no strength. There is a need for compositions andprocesses for flexible polyurethane elastomer foams to have hydrolyticstability in which the ratio of mechanical properties after hydrolysisdivided by that before hydrolysis should be above about 80 percent forboth tensile strength and percent elongation.

There is also a need for polyurethane compositions for athletic shoes toreceive and release high energy upon impact on striking a surface,thereby having superior energy return, in addition to a resilience whichis the ability to spring back into its original shape (elasticity) afterbeing compressed (measured by the rebound percentage). Athletic shoeslose massive amounts of energy due to shock impact, especially in areasaround the midsole. A well cushioned shoe helps disperse this shockimpact energy effectively thereby keeping the feet comfortable andpreventing them from hurting. The disclosed polyurethane foam-basedmidsoles have a number of desired characteristics, such as for example,a return energy of from about 50 percent to about 100 percent, fromabout 55 to about 75 percent, and from about 55 to about 65 percent asmeasured by VF Corporation with their proprietary equipment, hydrolyticstability, excellent resilience of, for example, from about 25 percentto about 60 percent, from about 30 percent to about 60 percent, fromabout 25 percent to about 45 percent, and improved compression sets.

Further, there is a need for polyurethane elastomers selected forinsoles and midsoles with excellent mechanical properties, and where theinsoles have in embodiments a density (gram/centimeters³) of, forexample, from about 0.2 to about 0.3; a hardness (Asker C) of, forexample, from about 15 to about 45; an elongation of from about 450percent to about 650 percent; a tensile strength of equal to or greaterthan about 20 MPa; a tear strength of equal to or greater than about 2Newtons/millimeters; a rebound test resilience of from about 40 to about55 percent; a compression set of equal to or less than about 6 percent;and a hydrolytic stability of equal to or at least 80 percent; and formidsoles, a density in gram/centimeter³ of less than about 0.5; ahardness (Asker C) of from about 30 to about 50; an elongation ofgreater than about 300 percent; a tensile strength in MPa of greaterthan about 10; a tear strength in Newtons/millimeters² of greater thanabout 3; a rebound test resilience of greater than about 60; acompression set of less than about 20 percent; an abrasion of less thanabout 300 percent; and a hydrolytic stability of at least 80 percent,and that are clear in color or white in color.

There is a need for athletic shoes with superior energy return, that isthe ability of footwear, such as athletic shoes, to receive and releaseenergy upon impact on striking the ground versus resilience, which isthe ability to spring back into its original shape (elasticity) afterbeing compressed and measured by the rebound percentage. Athletic shoes,whether for running or engaging in sports activities, lose massiveamounts of energy due to impact and shock, especially in the midsoles. Awell cushioned shoe disperses the impact and shock that keeps the feetcomfortable and prevents the feet from hurting. High performanceathletic shoes have well cushioned midsoles that transfer the impactinto forward motion or lift-offspring-like effect, as if theimpact/shock is being turned into a return energy. The disclosedpolyurethane foam-based midsoles have a number of desiredcharacteristics, such as for example, a return energy of from about 50percent to about 100 percent, from about 55 to about 75 percent, andfrom about 55 to about 65 percent as measured by VF Corporation withtheir proprietary equipment, hydrolytic stability, excellent resilienceof, for example, from about 25 percent to about 60 percent, from about30 percent to about 60 percent, from about 25 percent to about 45percent, and improved compression sets.

These and other needs can be achievable with the biobased plasticizerscontaining compositions polyurethane elastomers of the presentdisclosure.

SUMMARY

In embodiments of the present disclosure, there is disclosed aplasticizer for use in a variety of polymers to reduce its viscosity,increase flexibility and/or reduce the glass transition temperature ofthe polymer, and wherein the plasticizer is comprised of a biobaseddialkyl succinate or a biobased dialkyl sebacate, and wherein theplasticizers are derived from a biobased or biomass derived organic acidsuch as succinic acid, sebacic acid, dimer diacid, dodecanedioic acid,and a biomass or biobased derived organic alcohol such as methanol,ethanol, propanol, n-butanol, iso-butanol, 2-octanol, cardanol,ethoxylated cardanol, alkyl 12-hydroxy stearate and alkyl ricinolate.

There is provided in embodiments of the present disclosure biomass orbiobased plasticizers comprised of di-methyl succinate, di-ethylsuccinate or bis(ethyl) succinate, bis(n-butyl) succinate, bis(propyl)succinate, bis(2-butyl) succinate, bis(2-octyl) succinate, bis(cardanol)succinate, bis(ethoxy-cardanolyl) succinate, bis(12-alkyl stearyl)succinate, di-methyl sebacate, di-ethyl sebacate or bis(ethyl) sebacate,bis(n-butyl) sebacate, bis(propyl) sebacate, bis(2-butyl) sebacate,bis(2-octyl) sebacate, bis(cardanol) sebacate, bis(ethoxy-cardanolyl)sebacate, bis(12-alkyl stearylol) succinate, bis(12-alkyl stearylol)sebacate, bis(12-alkyl ricinoleyl) succinate, bis(12-alkyl ricinoleyl)sebacate, mixtures thereof, and the like.

Yet additionally, there are disclosed plasticizers comprised ofbis-alkyl succinate and bis-alkyl sebacate derived from theesterification of biobased diacids, such as succinic acid or sebacicacid, with a biobased alcohol, such as methanol, ethanol, propanol,n-butanol, iso-butanol, 2-octanol, cardanol, ethoxylated cardanol, alkyl12-hydroxy stearate and alkyl ricinolate, which can be especiallyselected for polyurethanes, such as polyurethane flexible foams (PU),for their applications as footwear, automotive parts, yoga mats,mattresses, and the like.

Further, there is disclosed a biomass derived from or biobased polyesterpolyols derived from a biobased diol, a biobased diacid and optionally abiobased organic acid-alcohol and polymers thereof, such as polyurethaneelastomers, derived from a di-isocyanate, a biobased polyester polyoland comprising biobased plasticizers, and wherein the bio-content of thepolyurethane elastomer is from about 70 to about 99 percent by weight.

Additionally, there is provided in embodiments of the presentdisclosure, biomass or biobased plasticizers, and wherein the estimateddifference in solubility parameter between the plasticizer and polymeris equal to or less than about 3 Mpa^(1/2), the solubility parameterbeing described in Hansen Solubility Parameters: A User's Handbook,Second Edition, CRC press, 2007 (ISBN9780429127526), the disclosure ofwhich is totally incorporated herein by reference.

Illustrated herein is also a biobased plasticizer comprised of acomponent selected from the group consisting of biobased bis-alkylsuccinate, bis-alkyl sebacate, and mixtures thereof, with specificexamples of biobased plasticizers being di-methyl succinate, diethylsuccinate, bis(ethyl) succinate, bis(n-butyl) succinate, bis(propyl)succinate, bis(2-butyl) succinate, bis(2-octyl) succinate, bis(cardanol)succinate, bis(ethoxy-cardanolyl) succinate, bis(12-alkyl stearyl)succinate, di-methyl sebacate, di-ethyl sebacate or bis(ethyl) sebacate,bis(n-butyl) sebacate, bis(propyl) sebacate, bis(2-butyl) sebacate,bis(2-octyl) sebacate, bis(cardanol) sebacate, bis(ethoxy-cardanolyl)sebacate, bis(12-alkyl stearylol) succinate, bis(12-alkyl stearylol)sebacate, bis(12-alkyl ricinoloyl) succinate, bis(12-alkyl ricinoloyl)sebacate, and mixtures thereof.

Also, disclosed is a composition comprised of a polymer and aplasticizer comprised of a component selected from the group consistingof biobased bis-alkyl succinate and biobased bis-alkyl sebacate.

Further, there are disclosed polyurethane elastomers comprised of aplasticizer comprised of a component selected from the group consistingof biobased bis-alkyl succinate and bis-alkyl sebacate, and a) anorganic diisocyanate, (b) a polyester resin, (c) a chain extender, (d) acrosslinker, (e) a surfactant, (f) an optional foaming agent, (g) anoptional colorant, and a (h) a catalyst, wherein the polyester can begenerated from the reaction of an organic diacid and an organic diol;wherein the foaming agent is present, the colorant is present and iscomprised of a dye or a pigment, and wherein said organic diisocyanateis selected from the group consisting of diphenylmethane4,4′-diisocyanate, isophorone diisocyanate, dicyclohexylmethane4,4-diisocyanate, hexamethylene 1,6-diisocyanate, naphthalene1,5-diisocyanate, and mixtures thereof.

Additionally, disclosed are biobased plasticizers comprised of bis-alkylsuccinate and bis-alkyl sebacate derived from the esterification ofbiobased diacid such as succinic acid or sebacic acid, and a biobasedalcohol such as ethanol, propanol, n-butanol, iso-butanol, 2-octanol,cardanol, ethoxylated cardanol, alkyl 12-hydroxy stearate and alkylricinolate, which plasticizers can be selected for the incorporationinto polyesters, polyols, polycarbonates, polyvinylchloride,polyurethane, polystyrene, polyamide, and wherein the energy differencebetween the solubility parameters of the polymer and plasticizer is, forexample, equal to or less than about 3 Mpa^(1/2).

Also, disclosed is a polyurethane elastomer with improvedcharacteristics that includes a biobased polyol polyester, which ishydrolytically stable, and is comprised of biobased polyester polyolswith a solubility parameter of, for example, from about 8 to about 10Mpa^(1/2), and a biobased plasticizer with a solubility parameter of,for example, from about 8 to about 10 Mpa^(1/2), and wherein thedifference in the solubility parameter between the polyester polyol andbiobased plasticizer is equal to or less than 5 Mpa^(1/2), less than 3Mpa^(1/2), or less than 1 Mpa^(1/2), such that optimal compatibility ofthese components is achieved.

Yet further disclosed herein are polyester polyols, such as a biomass orbiobased derived polyester polyols derived from the polycondensation oforganic diols with the number of carbon atoms being, for example, from 1to about 18, such as 1,2-propylene glycol, 1,3-propylene glycol,1,4-butylene glycol, dimer diols, and suitable organic diacids with thenumber of carbon atoms being from 1 to about 18, such as succinic acid,sebacic acid, dimer diacids, and optionally a suitable organicacid-alcohol, such as 12-hydroxy stearic acid and ricinoleic acid,copolymers, and terpolymers and the like.

Also, disclosed herein are polyurethane elastomer compositions, which inembodiments are comprised of and can be generated from the mixing andreacting of, or more specifically, obtained by mixing of and thenreacting (a) an organic diisocyanate, (b) a polyester resin, (c) a chainextender comprised of a polyhydric alcohol, (d) a crosslinker, (e) aplasticizer, (f) a surfactant, (g) a foaming agent, and (h) an optionalcolorant, such as a dye; and wherein the elastomers and foams thereofhave, for example, a hardness value of from about 15 or 20 Asker C toabout 60 Asker C; a tensile strength of, for example, from about 1 MPato about 10 MPa; a resilience of, for example, from about 25 percent toabout 60 percent; and an elongation at break of, for example, from about150 percent to about 700 percent, and a tear strength of, for example,from about 2 Newtons/millimeters to about 4 Newtons/millimeters, andwherein the polyurethane has a high biomass content of equal to orexceeding 75 percent by weight, and wherein the solubility parameter ofthe plasticizer, the polyester polyol and resulting polyurethaneelastomer have an energy difference between the solubility parameters ofthese components of equal to or less than about 3 Mpa^(1/2).

BRIEF DESCRIPTION OF DRAWINGS

Embodiments will now be described more fully with reference to theaccompanying drawings in which:

FIG. 1 is a plurality of structures of polyester resins in accordancewith the subject application; and

FIG. 2 is a plurality of structures of plasticizers in accordance withthe subject application.

EMBODIMENTS Polyesters

The disclosed biobased polyester polyol resins include the hydrophobicpolyester resins of FIG. 1 , and can be prepared by a polycondensationprocess by reacting suitable organic diols and suitable organic diacids,and optionally a suitable organic acid-alcohol in the presence ofpolycondensation catalysts. Generally, a stoichiometric equimolar ratioof organic diol and organic diacid is utilized, however, an excess oforganic diol can be selected such that the resulting polymer displays ahydroxyl number of from about 30 to about 60, an acid number of equal toor less than about 5 milligrams/gram of KOH, and more specifically, lessthan about 3 milligrams/gram of KOH, and with a molecular weight averageof from about 1,500 to about 5,000 Daltons as determined by GPC. In someinstances, where the boiling point of the organic diol is from, forexample, about 180° C. to about 230° C., an excess amount of diol, suchas an alkylene glycol like ethylene glycol or propylene glycol of fromabout 0.2 to 1 mole equivalent, can be utilized and removed during thepolycondensation process by distillation. The amount of catalystutilized varies, and can be selected in amounts as disclosed herein, andmore specifically, for example, from about 0.01 percent by weight toabout 1 percent by weight, or from about 0.1 to about 0.75 percent byweight based on the crystalline polyester resin.

Examples of organic diacids or diesters selected for the preparation ofthe amorphous polyester resins and the semicrystalline polyester resinsinclude succinic acid, fumaric acid, itaconic acid, glutaric acid,adipic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, C-18 dimer acids, such as 1,16-octadecanedioic acid,phthalic acid, isophthalic acid, terephthalic acid,naphthalene-2,6-dicarboxylic acid, naphathalene-2,7-dicarboxylic acid,cyclohexane dicarboxylic acid, malonic acid and mesaconic acid, anddiesters or anhydrides thereof. The organic diacid is selected in anamount of, for example, from about 40 to about 60 percent by weight ofthe polyester resin. The organic diacid selected can also be thoseobtained through fermentation processes, natural sources like chemicallyderived from natural (biobased) sources, such as succinic acid, fumaricacid, itaconic acid, sebacic acid, 1,12-dodecanedioic acid,2,5-furandicarboxylic acid, azelaic acid, dimer acids, which includealiphatic dimer acids with from about 2 carbon atoms to about 36 carbonatoms, such as C-18 dimer acids, or dimerized fatty acids ofdicarboxylic acids prepared by dimerizing unsaturated fatty acidsobtained from tall oil, usually on clay catalysts;hydrogenated/saturated dimer acids; and other known suitable organicacids.

The organic diol reactant selected can also be obtained from biomassesgenerated through fermentation processes, natural sources, andchemically derived from natural sources, and which reactant is, forexample, 1,5-pentanediol, 1,2-propanediol(1,2-propylene glycol),1,3-propanediol, 1,4-butanediol, 1,10-decanediol, 1,9-nonanediol, dimerdiols, which include aliphatic dimer diols with from about 2 carbonatoms to about 36 carbon atoms, such as PRIPOL® and aliphatic diolreactant examples with, for example, from about 2 carbon atoms to about36 carbon atoms, such as 1,2-ethanediol, 1,2-propanediol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,12-dodecanediol, 2-ethyl-2-butyl-1,3-propanediol, alkylene glycolslike ethylene glycol, propylene glycol, monoethylene glycol, diethyleneglycol, monopropylene glycol, dipropylene glycol, isosorbide, mixturesthereof, and the like. The organic diol is selected, for example, in anamount of from about 45 percent by weight to about 65 percent by weightof the polyester.

Examples of organic acid-alcohols selected for the preparation of theamorphous polyester resins and co-polyester resins as illustrated inFIG. 1 include 12-hydroxystearic acid, ricinoleic, and which is obtainedfrom natural sources and chemically derived from natural sources, and isoptionally selected, for example, in an amount of from about 5 percentby weight to about 100 percent by weight of the polyester. As will beunderstood, in FIG. 1 , a is an integer of from about 1 to about 10, andb is an integer of from about 1 to about 18; m, n and p are the randomsegments of the polyester resin (or copolymer); and wherein m is thesegment of the polyester resin derived from the organic diacid andorganic diol, and can be an integer of from about 10 to about 1,000random units of the polymer; n is the segment of the organicacid-alcohol (12-hydroxy stearic acid) with the copolymer containing them segment, and can be an integer of from about 0 to about 1,000 randomunits of the polymer; and p is the segment of the optional organicacid-alcohol (ricinoleic acid) with the copolymer containing the m unit,and can be an integer from about 0 to about 1,000 random units of thepolymer.

In embodiments of the present disclosure, examples of specific dimerdiols and dimer diacids are 12-hydroxystearic acids which enablesenhanced hydrophobic characteristics, and thus excellent hydrolyticallystable characteristics for the polyesters include, more specifically, asdimer acids PRIPOL® 1013, PRIPOL® 1017, PRIPOL® 1009, and PRIPOL® 1012,and the dimer diols, PRIPOL® 2033, and PRIPOL® 2043.

Biobased polyesters include those resins derived from biobased organicdiacids, diols and acid-alcohols, includingpoly(1,2-propylene-succinate), poly(1,2-propylene-sebacate),poly(1,3-propylene-succinate), poly(1,3-propylene-sebacate),poly(1,4-butylene-succinate), poly(1,4-butylene-sebacate),poly(1,2-propylene-azeleate), poly(1,2-propylene-azeleate),copoly(1,2-propylene succinate)-copoly(1,3-propylene succinate),copoly(1,2-propylene sebacate)-copoly(1,3-propylene sebacate),poly-12-hydroxy stearate, poly-riciniloate, copoly(1,2-propylenesuccinate)-copoly(12-hydroxy stearate),copoly(1,2-propylene-sebacate)-copoly(12-hydroxy stearate),copoly(1,3-propylene succinate)-copoly(12-hydroxy stearate),copoly(1,3-propylene sebacate)-copoly(12-hydroxy stearate),copoly(1,2-propylene succinate)-copoly(1,2-propylene sebacate),copoly(1,3-propylene succinate)-copoly(1,3-propylene sebacate),terpoly(1,2-propylenesuccinate)-terpoly(1,3-propylene-succinate)-terpoly(12-hydroxystearate), copoly(1,2-propylene succinate)-copoly(riciniloate),copoly(1,2-propylene-sebacate)-copoly(riciniloate), copoly(1,3-propylenesuccinate)-copoly(riciniloate), copoly(1,3-propylenesebacate)-copoly(12-ricinolate), terpoly(1,2-propylenesuccinate)-terpoly(1,3-propylene-succinate)-terpoly(12-hydroxystearate), terpoly(1,2-propylenesuccinate)-terpoly(1,3-propylene-succinate)-terpoly(riciniloate),mixture thereof and the like.

Specific biobased polyester polyols include those obtained from bioderived organic diols, such 1,2-propylene glycol, 1,3-propanediol, 1,4butanediol, isosorbide, dimer-diols, and bio derived diacids, such assuccinic acid, sebacic acid, adipic acid, furan-dioic acid,dodecanedioic acid, dimer diacid, and optionally a biobased organicacid-alcohol, such as 12-hydroxystearic acid or riciniloeic acid.

The polyester polyol and mixtures thereof can be present in thepolyurethane elastomer in various effective amounts of, for example,percent by weight of from about 1 to about 99, from about 10 to about85, from about 18 to about 75, from about 25 to about 65, from about 30to about 55, and from about 40 to about 60 based, for example, on thepolyurethane elastomer weight.

Catalysts

Examples of polycondensation catalysts primarily utilized for thepreparation of semicrystalline and amorphous polyesters includetetraalkyl titanates, dialkyltin oxide such as dibutyltin oxide,tetraalkyltin such as dibutyltin dilaurate, dialkyltin oxide hydroxidesuch as butyltin oxide hydroxide, aluminum alkoxides, alkyl zinc,dialkyl zinc, zinc oxide, stannous oxide, zinc acetate, titanium (iv)isopropoxide (Tyzor TE), tertiary amines, such as triethylamine,dimethylcyclohexylamine, N-methylmorpholine, N,N′-dimethylpiperazine,2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, DAPCO 33 LV(33 percent triethylenediamine dissolved in 67 percent dipropyleneglycol), BICAT 8109 (bismuth neodecanoate), Jeffcat-Zf-54(bis-(2-dimethylaminoethyl)ether in dipropylene glycol), KOSMOS® 75 MEG,and the like, organometallic compounds, such as titanic esters, ironcompounds, tin compounds, such as tin diacetate, tin dioctoate, tindilaurate, the dialkyl tin salts of aliphatic carboxylic acids likedibutyltin diacetate and dibutyltin dilaurate, other suitable catalysts,and the like. More specifically, catalysts utilized are comprised oforganometallic compounds like titanic esters, iron compounds, tincompounds, and other suitable known catalysts. Further, the differingcatalysts of copending application Ser. No. 17/015,669, the disclosureof which has been totally incorporated herein by reference, can beselected.

The catalysts can be selected in amounts of, for example, from about0.01 to about 5 percent by weight, from about 0.1 to about 0.8 percentby weight, and from about 0.2 to about 0.6 percent by weight, and othersuitable percentages based on the starting diacid or diester used togenerate the polyester resins.

In embodiments of the present disclosure, the catalysts selected for thesynthesis of the polyester resins, and that are used in the preparationof the polyurethane elastomer foams remain in, or are retained therein,thus purification processes may be avoided for the polyester synthesis,and products thereof, and for the polyurethane elastomer foams.

Plasticizers

The plasticizer is as disclosed herein and is comprised, for example, ofbiobased bis-alkyl succinates, or biobased bis-alkyl sebacate derivedfrom the esterification of biobased diacid, such as succinic acid orsebacic acid, with a biobased alcohol such as ethanol, propanol,n-butanol, iso-butanol, 2-octanol, cardanol, ethoxylated cardanol, alkyl12-hydroxy stearate and alkyl ricinolate, and wherein the alkyl group isfrom about 1 to about 12 carbon atoms such as methyl, ethyl, propyl,butyl, iso-butyl and 2-octanol.

The plasticizer can be prepared, for example, from the esterification ofbiobased diacid such as succinic acid or sebacic acid, and a biobasedalcohol such as ethanol, propanol, n-butanol, iso-butanol, 2-octanol,cardanol, ethoxylated cardanol, alkyl 12-hydroxy stearate and alkylricinolate. The alkyl 12-hydroxy stearate and alkyl ricinolate can beprepared from the esterification of 12-hydroxystearic acid or ricinoleicacid, and an alcohol such as methanol, ethanol, propanol, butanol,isobutanol or 2-octanol, and the like. Examples of the plasticizer aredepicted in FIG. 2 .

Crosslinkers

The crosslinker is, for example, selected from diethanolamine, glycerol,trimethylol propane, pentaerythritol, 1,2,4-butanetriol, thioglycolicacid, 2,6-dihydroxybenzoic acid, melamine, diglycolamine,1,2,6-hexanetriol, glycerol, 1,1,1-trimethylolethane,1,1,1-trimethylolpropane (TMP), triisopropanol amine, triethanol amine,tartaric acid, citric acid, malic acid, trimesic acid, trimellitic acid,trimellitic anhydride, pyromellitic acid, and pyromellitic dianhydride;trimethylolpropane, trimethylolethane; pentaerythritol, polyethertriols,tartaric acid, citric acid, malic acid, trimesic acid, trimellitic acid,trimellitic anhydride, pyromellitic acid, and pyromellitic dianhydride;trimethylolpropane, trimethylolethane; pentaerythritol, polyethertriols,and glycerol, and especially polyols, such as trimethylolpropane,pentaerythritol, and biobased materials thereof present in amounts of,for example, from about 0.1 percent by weight to about 10 percent byweight, and from about 0.1 percent by weight to about 5 percent byweight based on the amount of polyurethane elastomer, and other knownsuitable crosslinkers. The crosslinker in embodiments can be used toincrease the molecular weight of the polyurethane by interlinking thechains thereof to provide a more rigid network.

Chain Extenders

Chain extender examples include alcohols, such as polyhydric alcohols,carboxylic acid derivatives having two functional groups can be selectedfor the elastomers and processes disclosed herein. More specifically,chain extender examples contain, for example, two hydroxyl moieties suchas 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol,1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-ethyl-2-butyl1,3-propanediol; alkylene glycols like ethylene glycol, propyleneglycol, monoethylene glycol, diethylene glycol, monopropylene glycol,dipropylene glycol, mixtures thereof, other known suitable chainextenders, and the like present in amounts of, for example, from about0.1 percent by weight to about 10 percent by weight, from about 0.1percent by weight to about 5 percent by weight based on the polyurethaneelastomer, and other known suitable chain extenders. The chain extender,which can be a low molecular weight diol that reacts with a diisocyanateto provide for an increase in the block length of the polyurethane hardsegment without crosslinking of the chains thereof. The increase in theblock length of the polyurethane hard segment is usually proportional tothe amount of chain extender used, for example, from about 0.1 percentby weight to about 10 percent by weight.

Surfactants

The surfactants that can be selected are, for example,polyether-silicone oil mix (TEGOSTAB® B4113) available from Evonik,8383, silicone surfactant DABCO DC® 193, and TEGOSTAB® B8383 availablefrom Evonik, sodium dodecylbenzene sulfonate, sodium dodecylnaphthalenesulfate, dialkylbenzenealkyl, sulfates and sulfonates, adipic acid,available from Aldrich, NEOGEN R™, NEOGEN SC™, available from DaiichiKogyo Seiyaku, polyvinyl alcohol, polyacrylic acid, methalose, methylcellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose,carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylenelauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenylether, polyoxyethylene oleyl ether, polyoxyethylene sorbitanmonolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenylether, dialkylphenoxypoly(ethyleneoxy) ethanol, available from Rhodia asIGEPAL CA-210™, IGEPAL CA-520™, IGEPAL CA-720™, IGEPAL CO-890™, IGEPALCO-720™, IGEPAL CO-290™, ANTAROX 890™, and ANTAROX 897™, and othersuitable known surfactants in amounts of, for example, from about 0.1percent by weight to about 10 percent by weight, and from about 0.1percent by weight to about 3 percent by weight based on the polyurethaneelastomer amount.

Colorants

Colorant examples that can be selected for the preparation of thepolyurethane elastomer compositions present, for example, in amounts offrom about 1 percent by weight to about 10 percent by weight, 0.1percent by weight to about 5 percent by weight, and from about 0.1percent by weight to about 3 percent by weight based on the amount ofthe polyurethane elastomer include pigments, dyes, mixtures thereof, andthe like. Examples of dyes and pigments include inorganic pigments, suchas carbon black, whiteners, such as titanium oxide which has weatherresistance, and organic pigments and dyes, such as phthalocyanine blue,azo dyes, Indigo, Congo Red, Methyl Orange, Malachite Green, purpledyes, brown dyes, black dyes, Pigment Blue 15:3 or C.I. Pigment Blue15:4, phthalocyanine green, quinacridone red, indanthrene orange, andisoindolinone yellow, C.I. Pigment Red 254 and C.I. Pigment Red 122,C.I. Pigment Yellow 151 and C.I. Pigment Yellow 74, Fates Dye and KeenDye available from BAO Shen Polyurethane Tech.LTD-China, and othersuitable known colorants, such as known dyes and pigments illustrated inthe Color Index (C.I.), such as known magenta, yellow, and cyancolorants.

Foaming Agents

There is selected as the foaming (or blowing) agent water and othersuitable known blowing agents present in the reaction mixture and in theflexible polyurethane foams thereof, and which increases the firmness ofthe resulting foams. A soft, flexible, plasticized water-blownpolyurethane foam composition can be produced from the reaction of anatural polyol and methylene diphenyl diisocyanate, (MDI) or anequivalent isocyanate, and by optionally adding a plasticizer.

Specific examples of foaming agents include water, compressed gases,such as CO₂, N₂, air or low boiling liquids like cyclopentane, pentane,isobutane and hydrofluorocarbons, added in amounts of from about 0.03 toabout 10 percent by weight, and from about 0.5 percent by weight toabout 3 percent by weight of the polyurethane elastomer. Also, forexample, CO₂ may be generated insitu by the decomposition of NaHCO₃ orthe reaction of water with isocyanate.

Organic Diisocyanates

Examples of organic diisocyanates selected for the compositions andprocesses illustrated herein include aliphatic diisocyanates, such ashexamethylene diisocyanate, cycloaliphatic diisocyanates, such asisophorone diisocyanate, cyclohexane 1,4-diisocyanate,1-methylcyclohexane 2,4-diisocyanate, and 1-methylcyclohexane2,6-diisocyanate, and the corresponding isomer mixtures,dicyclohexylmethane 4,4′-diisocyanate, dicyclohexylmethane2,4′-diisocyanate, dicyclohexylmethane 2,2′-diisocyanate, and thecorresponding isomer mixtures, aromatic diisocyanates, such as tolylene2,4-diisocyanate, mixtures of tolylene 2,4-diisocyanate and tolylene2,6-diisocyanate, diphenylmethane 4,4′-diisocyanate, diphenylmethane2,4′-diisocyanate, and diphenylmethane 2,2′-diisocyanate, mixtures ofdiphenylmethane 2,4′-diisocyanate and diphenylmethane 4,4′-diisocyanate,urethane-modified liquid diphenylmethane 4,4′-diisocyanates ordiphenylmethane 2,4′-diisocyanates,4,4′-diisocyanato-1,2-diphenylethane, and naphthylene 1,5-diisocyanate.Especially selected diisocyanates are hexamethylene 1,6-diisocyanate,cyclohexane 1,4-diisocyanate, isophorone diisocyanate,dicyclohexylmethane diisocyanate, diphenylmethane diisocyanates withmore than 96 percent by weight content of diphenylmethane4,4′-diisocyanate, diphenylmethane 4,4′-diisocyanate, and naphthylene1,5-diisocyanate, suitable known diisocyanates, and mixtures thereof,and is selected in an amount of, for example, from about 10 percent byweight to about 40 percent by weight, and from about 15 percent byweight to about 25 percent by weight based on the polyurethane elastomeramount.

In embodiments, there can be selected mixtures of a diisocyanate and apolyisocyanate in an amount of up to about 15 percent by weight, basedon the total diisocyanates present, however, up to about 40 percent byweight of polyisocyanate can be added, and that provides an improvedthermoplastically processable product. Examples of polyisocyanatesinclude triisocyanates, biurets and isocyanurate trimer. For example,triphenylmethane 4,4′,4″-triisocyanate and polyphenylpolymethylenepolyisocyanates as well as hexamethylene diisocyanate (HDI) biurettrimer, isocyanurate trimer, and isophorone (IPDI) isocyanurate trimer.

The characteristics and properties of the polyurethane products can bemeasured as illustrated herein, and by known processes and devices. Morespecifically, there was selected as a tensile tester, the ADMET eXpert7601 Tensile Tester, to measure tensile strength, elongation, tearstrength and compression set, by preparing a sample of the polyurethaneelastomer, such as a foam material in dog-bone shapes with a die cutterwith a standard thickness of 10 millimeters and length of 140millimeters based on ASTM D412, ASTM D3574-17, SATRA TM-2 standards. Thesample removed was placed between clamps and where the tensile testerapplies the appropriate force at a particular speed (generated by thesoftware) on the test material sample to provide the characteristics,properties and values of the polyurethane products.

Density was measured using the equation Density=Mass/Volume, where massrepresents the mass of the material in a mold measured on an analyticalbalance. Volume of the mold was obtained from the dimensions of themold. For example, if a mold was producing 10 millimeters or 1centimeter polyurethane foam plaques with dimensions length equal to 21centimeters, width equal to 14.8 centimeters, and the thickness equal to10 millimeters, then volume was calculated to be 21 times 14.8 times 1equals 310.80 centimeters³.

The hardness can be measured on the Asker C scale, and can also bemeasured by a durometer.

Bio-Content

The bio-content of the disclosed polyurethane elastomer foams can bedetermined by various methods. In one method, the bio-content can bemeasured as follows and where, for example, the biobased polyesterpolyol, biobased plasticizer, optionally, and biobased chain extenderwhich also impart bio-content characteristics to the polyurethaneelastomer foams.

Thus, based on the bio-content of the ingredients present in thepolyurethane foam formulations, the bio-content for the polyurethaneelastomer foam is, for example, from about 60 percent to about 90percent, from about 40 percent to about 85 percent, from about 70percent to about 85 percent, and from about 70 percent to about 80percent.

More specifically, although it is not desired to be limited by theory,generally, for the polyurethane plasticizer foam preparation inembodiments and the appropriate Examples that follow the active reactantcomponents of, for example, the polyester resin, the crosslinker, thechain extender, and the foaming agent, and the nonreactive componentsof, for example, dye, plasticizer, and surfactant are initially admixedfollowed by the addition of the organic diisocyanate and heating. Thepolyester that contains at least one hydroxyl end group, that is thepolyester polyol, reacts with the diisocyanate resulting in a urethanelinkage. The chain extender of, for example, 1,3-propanediol which alsohas hydroxyl ends reacts with the diisocyanate to generate urethanelinkages. The crosslinker of, for example, diethanol amine includes twohydroxyl moieties and one amine (N—H) moiety, and where all 3functionalities react with the diisocyanate to form either the urethaneor urea linkage, respectively. Finally, the foaming agent like waterreacts with the diisocyanate to result in an amine, and that aminefurther reacts with the diisocyanate to give the urea linkage. Theelastomer foam can be referred to as a polyurethane, however, it isknown and accepted that when a crosslinker like diethanolamine, and thefoam agent like water are present there will be some urea linkages,albeit very small, such as less than about 3.5 percent.

TEGOSTAB® B4113 and B8383 are considered silicone surfactants; CA-210 isa surfactant of octylphenoxy poly(ethyleneoxy)ethanol; CA-520 is apolyoxyethylene (5) isooctylphenyl ether surfactant; ANTAROX® 890 is apolyoxyethylene (40) nonylphenyl ether surfactant; and ANTAROX® 897 is apoly(oxy-1,2-ethanediyl), α-(nonylphenyl)-ω-hydroxy surfactant.

Polyester polyol PSA300 is a polyester polyol with a weight averagemolecular weight of about 3,000; ISO is diisocyanate, a commerciallyavailable diisocyanate SUPRASEC™ 2379; MDI is diphenyl methanediisocyanate (MDI); and FATES® dye is an orange polyester dye that iscommercially available. The chemical name for FATES® dye has not beendisclosed by the supplier. Further, examples of dyes are timerlandorange, timerland lime green, timerland dark cheddar, all available fromBAO Shen Polyurethane Tech.LTD-China; and DABCO® 33LV is an aminecatalyst of 33 percent TEDA (triethylene diamine) dissolved indipropylene glycol. Abrasion refers to a material's ability to withstandwear as it encounters friction.

Specific embodiments of the present disclosure as illustrated in thefollowing Examples are for illustrative purposes and are not limited tothe materials, conditions, or process parameters set forth in theseembodiments. Parts and percentages are by weight unless otherwiseindicated. Also, the components can be mixed in various sequences toobtain the plasticizers, the polyurethane elastomers and thepolyurethane foams, which can be biodegradable. The viscosities weremeasured by the Brookfield CAP2000 Viscometer. A footbed mold refers toa mold with a cavity of certain design replicating an insole or amidsole of footwear like a shoe. The cavity has a certain volume whenthe formulation mixture poured and closed to form the foam product.

Example 1

Preparation of a plasticizer comprised of biobased di-n-butyl succinate.

To a 500 milliliter 3-necked flask equipped with a mechanical stirrerand a dean-stark distillation apparatus were added 100 grams of biobasedsuccinic acid (obtained from Bio-Amber), 139 grams of biobased n-butanol(available from Butamax) and 0.1 gram of methane sulfonic acid catalyst.The resulting mixture under a nitrogen atmosphere was heated to 130° C.over a 90 minute period, where 25 grams of distillate comprised of waterand n-butanol were collected in the distillation receiver. The flask wasthen cooled to 110° C. and an additional 50 grams of n-butanol wereadded. The mixture obtained was then heated to 155° C., maintained fortwo hours at this temperature, and more distillate was obtained. Theflask was then cooled to 110° C., and another 50 grams of n-butanol wereadded, and the resulting mixture reheated to 155° C. for 4 more hoursand until no more distillate condensed. The acid value of the product,measured using the ASTM D974 procedure, was 0.5 milligram of KOH/gram.The product, biobased di-n-butyl succinate, was then cooled to roomtemperature, about 25° C. throughout, and filtered through a glassfilter frit (G-3 pore) equipped with 2 paper filters (medium pore) intoa 250 milliliter filtration flask under slight vacuum to result in 188grams of clear liquid. The identity of the biobased di-n-butyl succinateproduct was confirmed by NMR spectroscopy.

Example 2

Preparation of a plasticizer comprised of biobased bis(2-octyl)succinate.

To a 250 milliliter 3-necked flask equipped with a magnetic stirrer anda dean-stark distillation apparatus were added 50 grams of biobasedsuccinic acid (obtained from Bio-Amber), 110 grams of biobased2-octanol, obtained from Arkema and 0.2 gram of titanium (IV)iso-propoxide catalyst, obtained from Sigma. The resulting mixture undera nitrogen atmosphere was heated to 185° C. over a 4 hour period andmaintained 185° C. until the acid value of the mixture was measured tobe <1.0 milligram of KOH/gram. Nitrogen was then bubbled through thereaction mixture for an additional 30 minutes, after which the product,biobased bis(2-octyl) succinate, was cooled to room temperature and thenfiltered through a glass filter frit (G-3 pore) equipped with 2 paperfilters (medium pore) into a 250 milliliter filtration flask underslight vacuum to result in 188 grams of clear liquid of biobasedbis(2-octyl) succinate product, confirmed by NMR spectroscopy.

Example 3

Preparation of a plasticizer comprised of biobasedbis(ethoxy-cardanolyl) succinate.

To a 250 milliliter 3-necked flask equipped with a magnetic stirrer anda dean-stark distillation apparatus were added 29.5 grams of biobasedsuccinic acid (obtained from Bio-Amber), 177.4 grams of biobasedethoxylated cardanol (obtained as LITE 2020™ from CardoliteCorporation), and 0.2 gram of titanium (IV) iso-propoxide catalyst. Theresulting mixture under nitrogen atmosphere was heated to 190° C. over a4 hour period and maintained at 190° C. until the acid value of themixture was measured to be less than about 1.0 milligram of KOH/gram.Nitrogen was then bubbled through the reaction mixture for an additional30 minutes, after which the product, biobased bis(ethoxy-cardanolyl)succinate, was cooled to room temperature and then filtered through aglass filter frit (G-3 pore) equipped with 2 paper filters (medium pore)into a 250 milliliter filtration flask under slight vacuum to result in196 grams of clear liquid of the biobased bis(ethoxy-cardanolyl)succinate as confirmed by NMR spectroscopy.

Example 4

Preparation of a plasticizer comprised of biobased bis(2-octyl)sebacate.

To a 250 milliliter 3-necked flask equipped with a magnetic stirrer anda dean-stark distillation apparatus were added 90.1 grams of biobasedsebacic acid (obtained from Oleris Arkema), 127.5 grams of biobased2-octanol (obtained from Oleris Arkema) and 0.2 gram of titanium (IV)iso-propoxide catalyst. The mixture under nitrogen atmosphere was heatedto 185° C. over a 4 hour period and maintained at 185° C. until the acidvalue of the mixture was measured to be <1.0 milligram of KOH/gram.Nitrogen was then bubbled through the reaction mixture for an additional30 minutes, after which the product, biobased bis(2-octyl) sebacate, wascooled to room temperature and then filtered through a glass filter frit(G-3 pore) equipped with 2 paper filters (medium pore) into a 250milliliter filtration flask under slight vacuum to result in 188 gramsof a clear liquid product of biobased bis(2-octyl) sebacate as confirmedby NMR spectroscopy.

Example 5

Preparation of a plasticizer comprised of biobasedbis(ethoxy-cardanolyl) sebacate.

To a 250 milliliter 3-necked flask equipped with a magnetic stirrer anda dean-stark distillation apparatus were added 29.5 grams of biobasedsebacic acid (obtained from Oleris Arkema), 177.4 grams of biobasedethoxylated cardanol (obtained as LITE 2020™ from CardoliteCorporation), and 0.2 gram of titanium (IV) iso-propoxide catalyst. Themixture under nitrogen atmosphere was heated to 190° C. over a 4 hourperiod and maintained at 190° C. until the acid value of the mixture wasmeasured to be <1.0 milligram of KOH/gram. Nitrogen was then bubbledthrough the resulting reaction mixture for an additional 30 minutes,after which the product, biobased bis(ethoxy-cardanolyl) sebacate, wascooled to room temperature and then filtered through a glass filter frit(G-3 pore) equipped with 2 paper filters (medium pore) into a 250milliliter filtration flask under slight vacuum to result in 196 gramsof a clear liquid of biobased bis(ethoxy-cardanolyl) sebacate product,as confirmed by NMR spectroscopy.

Example 6

Preparation of the biobased polyester resin poly(1,3 propylenesuccinate) derived from 1 mole equivalent of succinic acid, and 1.1 moleequivalent of 1,3-propanediol.

To a 500 milliliter 3-necked flask equipped with a magnetic stirrer anddistillation apparatus were added 130.6 grams of biobased 1,3propanediol (available from DuPont), 184.6 grams of biobased succinicacid (available from Bioamber), and 0.1 gram of titanium (IV)isopropoxide catalyst. The obtained mixture was kept under nitrogen andheated to 190° C. for over 220 minutes with stirring at 250 rpm, andmaintained at 190° C. for 7 additional hours wherein about 52 grams ofwater collected in the distillation receiver. The flask was then leftcooling to room temperature, resulting in a viscous clear liquid productcomprised of biobased poly(1,3, propylene succinate). The acid value wasmeasured to be 0.85 milligram of KOH/g using the ASTM D974 procedure.The viscosity was measured to be 3,294 centipoise using the BrookfieldCAP2000 Viscometer at 70° C.

Example 7

Preparation of the biobased polyester resin poly(1,3 propylenesuccinate) derived from 1 mole equivalent of succinic acid, and 1.1 moleequivalent of 1,3-propanediol.

To a 500 milliliter 3-necked flask equipped with a magnetic stirrer anddistillation apparatus were added 130.6 grams of biobased1,3-propanediol (available from Dupont), 184.6 grams of biobasedsuccinic acid (available from Bioamber), and 0.1 gram of titanium (IV)isopropoxide catalyst. The mixture obtained was kept under nitrogen andheated to 190° C. for over 220 minutes with stirring at 250 rpm, andmaintained at 190° C. for 7.5 additional hours wherein about 67.5 gramsof water collected in the distillation receiver. The flask was then leftcooling to room temperature resulting in a viscous clear liquid productcomprised of biobased poly(1,3 propylene succinate). The acid value wasmeasured to be 1.91 milligrams of KOH/gram using the ASTM D974procedure. The viscosity was measured to be 4,852 centipoise using theBrookfield CAP2000 Viscometer at 70° C.

Example 8

Preparation of the biobased polyester resin copoly(1,2 propylenesuccinate)-copoly(1,3-propylene succinate), derived from 1 moleequivalent of succinic acid, 0.5 mole equivalent of 1,2-propyleneglycol, and 0.5 mole equivalent of 1,3-propanediol.

To a 500 milliliter 3-necked flask equipped with a magnetic stirrer anddistillation apparatus were added 74.5 grams of biobased 1,3-propanediol(available from Dupont), 74.5 grams of biobased 1,2-propylene glycol(available from Archer Daniels Midland), 210 grams of biobased succinicacid (available from Bioamber), and 1.0 gram of titanium (IV)isopropoxide catalyst. The mixture was heated to 180° C. over 120minutes with stirring at 250 rpm, and maintained at 180° C. for 5additional hours, after which an additional amount of 20 grams of1,3-propanediol were added and maintained at 180° C. for an additional 6hours. The flask was then left cooling to room temperature resulting ina viscous clear liquid product comprised of biobased copoly(1,2propylene succinate)-copoly(1,3-propylene succinate). The acid value wasmeasured to be 5.41 milligrams of KOH/gram using the ASTM D974procedure. The viscosity was measured to be 6,693 centipoises using theBrookfield CAP2000 Viscometer at 70° C.

Example 9

Preparation of the biobased polyester resin copoly(1,3-propylenesuccinate), copoly(12-hydroxy-stearate) derived from 0.95 moleequivalent of succinic acid, 0.1 mole equivalent of 12-hydroxy stearicacid, and 0.96 mole equivalent of 1,3-propanediol.

To a 500 milliliter 3-necked flask equipped with a magnetic stirrer anddistillation apparatus were added 136 grams of biobased 1,3-propanediol(available from DuPont), 51.6 grams of biobased 12-hydroxystearic acid(available from Archer Daniels Midland), 210 grams of biobased succinicacid (available from Blachford), and 0.4 gram of methane sulfonic acidcatalyst. The mixture obtained was heated to 175° C. over 180 minuteswith stirring at 250 rpm, and then heated to 200° C. over 15 minutes,and maintained at 200° C. for an additional 3 hours. About 69 grams ofwater were collected in the distillation receiver. The flask was thenleft cooling to room temperature resulting in a viscous clear liquidproduct comprised of biobased copoly(1,3-propylene succinate),copoly(12-hydroxy-stearate). The acid value was measured to be 1.78milligrams of KOH/gram using the ASTM D974 procedure. The viscosity wasmeasured to be 1,260 centipoises using the Brookfield CAP2000 Viscometerat 70° C.

Example 10

Preparation of the biobased polyester resin copoly(1,3-propylenesuccinate), copoly(12-hydroxy-stearate) derived from 0.925 moleequivalent of succinic acid, 0.15 mole equivalent of 12-hydroxy stearicacid, and 1.025 mole equivalent of 1,3-propanediol.

To a 500 milliliter 3-necked flask equipped with a magnetic stirrer anddistillation apparatus were added 125 grams of biobased 1,3-propanediol(available from DuPont), 79 grams of biobased 12-hydroxystearic acid(available from Archer Daniels Midland), 175.9 grams of biobasedsuccinic acid (available from Blachford), and 0.4 gram of methanesulfonic acid catalyst. The mixture was heated to 200° C. over 90minutes with stirring at 250 rpm, and maintained at 200° C. for anadditional 5 hours. About 55 grams of water were collected in thedistillation receiver. The flask was then left cooling to roomtemperature resulting in a viscous clear liquid product comprised ofbiobased copoly(1,3-propylene succinate), copoly(12-hydroxy-stearate).The acid value was measured to be 1.32 milligrams of KOH/gram using theASTM D974 procedure. The viscosity was measured to be 2,700 centipoisesusing the Brookfield CAP2000 Viscometer at 70° C.

Example 11

Preparation of the biobased polyester resin copoly(1,3-propylenesuccinate), copoly(12-hydroxy-stearate) derived from 0.875 moleequivalent of succinic acid, 0.25 mole equivalent of 12-hydroxy stearicacid, and 0.975 mole equivalent of 1,3-propanediol.

To a 500 milliliter 3-necked flask equipped with a magnetic stirrer anddistillation apparatus were added 125 grams of biobased 1,3-propanediol(available from DuPont), 79 grams of biobased 12-hydroxystearic acid(available from Archer Daniels Midland), 175.9 grams of biobasedsuccinic acid (available from Blachford), and 0.4 gram of methanesulfonic acid catalyst. The mixture resulting was heated to 185° C. over90 minutes with stirring at 250 rpm, and then heated at 200° C. over 60minutes, and maintained at 200° C. for an additional 4 hours. About 47grams of water were collected in the distillation receiver. The flaskwas then left cooling to room temperature resulting in a viscous clearliquid product comprised of biobased copoly(1,3-propylene succinate),copoly(12-hydroxy-stearate). The acid value was measured to be 1.36milligrams of KOH/gram using the ASTM D974 procedure. The viscosity wasmeasured to be 2,033 centipoises using the Brookfield CAP2000 Viscometerat 70° C.

Example 12

Preparation of an insole plaque polyurethane foam derived from 60.3weight percent of the biobased polyester resin of Example 6, 12.1 weightpercent of the biobased diethyl succinate plasticizer, 22.3 weightpercent of diisocyanate, 1.77 weight percent of chain extender, 2 weightpercent of dye, 0.6 weight percent of catalyst, 0.33 weight percent ofsurfactant, 0.06 weight percent of crosslinker, and 0.53 weight percentof water.

60.3 Grams of the polyester resin of Example 6 were melted in a 400milliliter glass can at 70° C. for 2 hours in an oven. To this was added0.33 gram of TEGOSTAB® surfactant (available from Evonik), 1.77 grams of1,3-propanediol (chain extender), 0.6 gram of DABCO LV® catalyst(available from Evonik), 0.53 gram of water, 0.06 gram of diethanolamine crosslinker, 2 grams of Red dye (available from BAO ShenPolyurethane Tech. LTD-China), 12.1 grams of biobased diethyl succinate,and the resulting mixture was stirred for 30 minutes at 2,000 rpm toensure homogeneity. The mixture was then added to the empty glass canand stirred for 4 minutes at 2,000 rpm to form a dispersion. Whilestirring, 22.33 grams of a diisocyanate (available from Huntsman asRubinate 1680) were injected into the resulting dispersion via apre-weighed syringe. After the syringe was empty, the mixture resultingwas stirred for a further 5 seconds, and 99.5 grams of this mixture werethen poured into a plaque mold which had a volume of 311 centimeters³(21 centimeters Length×18.8 centimeters Width×1 centimeter Thickness).The mold temperature was at 50° C. to 55° C., and the curing time was 30minutes resulting in a plaque density of about 0.315 gram/centimeters³.Subsequently, the plaques were tested for mechanical properties aftercutting into appropriate dog-bone shapes according to ASTM D3574. Themechanical properties are listed in Table 1. The bio-content of thisplaque was 74.2 percent by weight.

The above foam is also tested for hydrolytic stability according to thefollowing procedure. Plastic bottles (300 milliliters) are filled withdistilled water (200 milliliters), and the above prepared dog-boneshaped foam material is hung using a string ensuring the foam materialis completely immersed into the water. The product obtained is thenplaced in the oven and kept there for 2 weeks while maintaining thetemperature in the range of 65° C. to 70° C. After the test period, asample is removed from the water and dried in the oven at about 70° C.The ratio of mechanical properties after hydrolysis, divided by thatbefore hydrolysis should be above about 80 percent for both tensilestrength and percent elongation. For the polyurethane plaque of thisExample, the stability is found to be 85 percent for tensile strengthand 125 percent for elongation.

Example 13

Preparation of an insole plaque polyurethane foam derived from 56.8weight percent (percent by weight) of polyol, 17.1 weight percent of thebiobased diethyl succinate plasticizer, 21.1 weight percent ofdiisocyanate, 1.66 weight percent of chain extender, 2 weight percent ofdye, 0.57 weight percent of catalyst, 0.31 weight percent of surfactant,0.06 weight percent of crosslinker, and 0.5 weight percent of water.

56.8 Grams of the polyester resin of Example 6 were melted in a 400milliliter glass can at 70° C. for 2 hours in an oven. To this was added0.31 gram of TEGOSTAB® surfactant (available from Evonik), 1.6 grams of1,3-propanediol (chain extender), 0.57 gram of DABCO LV® catalyst(available from Evonik), 0.5 gram of water, 0.06 gram of diethanol aminecrosslinker, 2 grams of Red dye (available from BAO Shen PolyurethaneTech. LTD-China), 17.05 grams of biobased diethyl succinate, and theresulting mixture was stirred for 30 minutes at 2,000 rpm to ensurehomogeneity. The mixture was then added to the empty glass can andstirred for 4 minutes at 2,000 rpm to form a dispersion. While stirring,21.05 grams of a diisocyanate (available from Huntsman as Rubinate 1680)were injected into the resulting dispersion via a pre-weighed syringe.After the syringe was empty, the mixture resulting was stirred for afurther 5 seconds, and 99.5 grams of this mixture were then poured intoa plaque mold, which had a volume of 311 centimeters³ (21 centimetersLength×18.8 centimeters Width×1 centimeters Thickness). The moldtemperature was at 50° C. to 55° C., and the curing time was 30 minutesresulting in a plaque density of about 0.315 gram/centimeters³.Subsequently, the plaques were tested for mechanical properties aftercutting into appropriate dog-bone shapes according to ASTM D3574. Themechanical properties are listed in Table 1. The bio-content of thisplaque was 75.5 percent by weight. For the polyurethane plaque of thisExample, the hydrolytic stability using the procedure as described inExample 12 is found to be 83 percent for tensile strength and 120percent for elongation.

TABLE 1 Mechanical Performance of the Polyurethane Plaques Die C SplitDensity Hardness Rebound Tear Tear Strength Elongation Examples (g/cm³)(Asker C) (%) (N/mm) (N/mm) (ksc) (%) Example 12 0.315 36 42 7.0 1.413.1 346 Example 13 0.315 32 53 5.6 1.32 10.5 335

Example 14

Preparation of an insole plaque polyurethane foam derived from 57.1weight percent of polyol, 17.1 weight percent of the biobased dibutylsuccinate plasticizer, 20.8 weight percent of diisocyanate, 1.67 weightpercent of chain extender, 2 weight percent of dye, 0.29 weight percentof catalyst, 0.31 weight percent of surfactant, 0.06 weight percent ofcrosslinker, and 0.57 weight percent of water.

84 Grams of the polyester resin of Example 9 were melted in a 400milliliter glass can at 70° C. for 2 hours in an oven. To this was added0.462 gram of TEGOSTAB® surfactant (available from Evonik), 2.46 gramsof 1,3-propanediol (chain extender), 0.42 gram of DABCO LV® catalyst(available from Evonik), 0.84 gram of water, 0.084 gram of diethanolamine crosslinker, 2.95 grams of Orange dye (available from BAO ShenPolyurethane Tech. LTD-China), 25.2 grams of biobased dibutyl succinateof Example 1, and the resulting mixture was stirred for 30 minutes at2,000 rpm to ensure homogeneity. The mixture was then added to the emptyglass can and stirred for 4 minutes at 2,000 rpm to form a dispersion.While stirring, 30.64 grams of a diisocyanate (available from Huntsmanas Rubinate 1680) were injected into the resulting dispersion via apre-weighed syringe. After the syringe was empty, the mixture resultingwas stirred for a further 5 seconds, and 124.4 grams of this mixturewere then poured into a plaque mold which had a volume of 311centimeters³ (21 centimeters Length×18.8 centimeters Width×1 centimetersThickness). The mold temperature was at 50° C. to 55° C., and the curingtime was 30 minutes resulting in a plaque density of about 0.4gram/centimeters³. Subsequently, the plaques were tested for mechanicalproperties after cutting into appropriate dog-bone shapes according toASTM D3574. The mechanical properties are listed in Table 2. Thebio-content of this plaque was 76 percent by weight. For thepolyurethane plaque of this Example, the hydrolytic stability using theprocedure as described in Example 12 is found to be 90 percent fortensile strength and 130 percent for elongation.

TABLE 2 Mechanical Performance of the Polyurethane Plaques Die C SplitDensity Hardness Rebound Tear tear Strength Elongation Examples (g/cm³)(Asker C) (%) (N/mm) (N/mm) (ksc) (%) Example 14 0.4 34 35 4.2 1.1 0.76194

Example 15

Preparation of a plaque polyurethane foam derived from 64.9 weightpercent of polyol, 6.6 weight percent of the biobasedbis(ethoxy-cardanolyl) sebacate plasticizer, 22.9 weight percent ofdiisocyanate, 1.9 weight percent of chain extender, 2.3 weight percentof dye, 0.65 weight percent of catalyst, 0.36 weight percent ofsurfactant, 0.07 weight percent of crosslinker, and 0.57 weight percentof water.

96 Grams of the polyester resin of Example 10 were melted in a 400milliliter glass can at 70° C. for 2 hours in an oven. To this was added0.528 gram of TEGOSTAB® surfactant (available from Evonik), 2.81 gramsof 1,3-propanediol (chain extender), 0.96 gram of DABCO LV® catalyst(available from Evonik), 0.845 gram of water, 0.096 gram of diethanolamine crosslinker, 3.37 grams of Orange dye (available from BAO ShenPolyurethane Tech. LTD-China), 9.66 grams of biobasedbis(ethoxy-cardanolyl) sebacate of Example 5, and the resulting mixturewas stirred for 30 minutes at 2,000 rpm to ensure homogeneity. Themixture was then added to the empty glass can and stirred for 4 minutesat 2,000 rpm to form a dispersion. While stirring, 33.69 grams of adiisocyanate (available from Huntsman as Rubinate 1680) were injectedinto the resulting dispersion via a pre-weighed syringe. After thesyringe was empty, the mixture resulting was stirred for a further 5seconds, and 124.4 grams of this mixture are then poured into a plaquemold which had a volume of 311 centimeters³ (21 centimeters Length×18.8centimeters Width×1 centimeters Thickness). The mold temperature was at50° C. to 55° C., and the curing time was 30 minutes resulting in aplaque density of about 0.4 gram/centimeters³. Subsequently, the plaqueswere tested for mechanical properties after cutting into appropriatedog-bone shapes according to ASTM D3574. The mechanical properties arelisted in Table 3. The bio-content of this plaque was 73.4 percent byweight. For the polyurethane plaque of this Example, the hydrolyticstability using the procedure as described in Example 12, is found to be90 percent for tensile strength and 125 percent for elongation.

Example 16

Preparation of a plaque polyurethane foam derived from 63.75 weightpercent of polyol, 6.38 weight percent of the biobasedbis(ethoxy-cardanolyl) sebacate plasticizer, 24.1 weight percent ofdiisocyanate, 1.87 weight percent of chain extender, 2.24 weight percentof dye, 0.56 weight percent of catalyst, 0.35 weight percent ofsurfactant, 0.06 weight percent of crosslinker, and 0.56 weight percentof water.

94 Grams of the polyester resin of Example 11 were melted in a 400milliliter glass can at 70° C. for 2 hours in an oven. To this was added0.517 gram of TEGOSTAB® surfactant (available from Evonik), 2.75 gramsof 1,3-propanediol (chain extender), 0.94 gram of DABCO LV® catalyst(available from Evonik), 0.827 gram of water, 0.094 gram of diethanolamine crosslinker, 3.3 grams of Orange dye (available from BAO ShenPolyurethane Tech. LTD-China), 9.4 grams of biobasedbis(ethoxy-cardanolyl) sebacate of Example 5, and the resulting mixturewas stirred for 30 minutes at 2,000 rpm to ensure homogeneity. Themixture was then added to the empty glass can and stirred for 4 minutesat 2,000 rpm to form a dispersion. While stirring, 35.6 grams of adiisocyanate (available from Huntsman as Rubinate 1680) were injectedinto the resulting dispersion via a pre-weighed syringe. After thesyringe was empty, the mixture resulting was stirred for a further 5seconds, and 124.4 grams of this mixture were then poured into a plaquemold which had a volume of 311 centimeters³ (21 centimeters Length×18.8centimeters Width×1 centimeters Thickness). The mold temperature was at50° C. to 55° C., and the curing time was 30 minutes resulting in aplaque density of about 0.4 gram/centimeters³. Subsequently, the plaqueswere tested for mechanical properties after cutting into appropriatedog-bone shapes according to ASTM D3574. The mechanical properties arelisted in Table 3. The bio-content of this plaque was 72.1 percent byweight. For the polyurethane plaque of this Example, the hydrolyticstability using the procedure as described in Example 12 is found to be95 percent for tensile strength and 125 percent for elongation.

Example 17

Preparation of a plaque polyurethane foam derived from 62.9 weightpercent of polyol, 6.29 weight percent of the biobasedbis(ethoxy-cardanolyl) sebacate plasticizer, 25.1 weight percent ofdiisocyanate, 1.85 weight percent of chain extender, 2.21 weight percentof dye, 0.63 weight percent of catalyst, 0.35 weight percent ofsurfactant, 0.06 weight percent of crosslinker, and 0.55 weight percentof water.

94 Grams of the polyester resin of Example 9 were melted in a 400milliliter glass can at 70° C. for 2 hours in an oven. To this was added0.484 gram of TEGOSTAB® surfactant (available from Evonik), 2.58 gramsof 1,3-propanediol (chain extender), 0.88 gram of DABCO LV® catalyst(available from Evonik), 0.774 gram of water, 0.088 gram of diethanolamine crosslinker, 3.09 grams of Orange dye (available from BAO ShenPolyurethane Tech. LTD-China), 8.8 grams of biobasedbis(ethoxy-cardanolyl) sebacate of Example 5, and the resulting mixturewas stirred for 30 minutes at 2,000 rpm to ensure homogeneity. Themixture was then added to the empty glass can and stirred for 4 minutesat 2,000 rpm to form a dispersion. While stirring, 35.1 grams of adiisocyanate (available from Huntsman as Rubinate 1680) were injectedinto the resulting dispersion via a pre-weighed syringe. After thesyringe was empty, the mixture resulting was stirred for a further 5seconds and 124.4 grams of this mixture were then poured into a plaquemold which had a volume of 311 centimeters³ (21 centimeters Length×18.8centimeters Width×1 centimeters Thickness). The mold temperature was at50° C. to 55° C., and the curing time was 30 minutes resulting in aplaque density of about 0.4 gram/centimeters³. Subsequently, the plaqueswere tested for mechanical properties after cutting into appropriatedog-bone shapes according to ASTM D3574. The mechanical properties arelisted in Table 3. The bio-content of this plaque was 71.1 percent byweight. For the polyurethane plaque of this Example, the hydrolyticstability using the procedure as described in Example 12 was found to be90 percent for tensile strength and 120 percent for elongation.

TABLE 3 Mechanical Performance of the Polyurethane Plaques Die C SplitDensity Hardness Rebound Tear tear Strength Elongation Examples (g/cm3)(Asker C) (%) (N/mm) (N/mm) (ksc) (%) Example 15 0.4 30-35 30-35 4.0-4.51.5-2.0 2.5-3.0 200-250 Example 16 0.4 35-40 35-40 4.5-5.0 1.5-2.03.0-3.5 250-300 Example 17 0.4 35-40 40-45  6.0-v7.0 2.0-2.5 3.0-3.5300-350 Example 18 0.4 35-40 35-40 5.5-6.0 2.0-2.5 3.0-3.5  25-300

Specific embodiments of the present disclosure as illustrated in thefollowing Examples are for illustrative purposes and are not limited tothe materials, conditions, or process parameters set forth in theseembodiments. Percent by weight is a known quantity and is usually basedon the total of the components present. Molecular weights were providedby the sources involved, or by GPC, and from about to about includes allthe values in between and some values that exceed or may not exceed thevalues disclosed. Also, the components of (a) to (h) can be mixed invarious sequences to obtain the polyurethane elastomers and thepolyurethane foams, both of which can be biodegradable. The viscositieswere measured by the Brookfield CAP2000 Viscometer.

What is claimed is:
 1. A polyurethane elastomer derived from: aplasticizer comprising a biobased bis(ethyl) succinate; a biobasedpolyester resin comprising terpoly(1,2-propylenesuccinate)-terpoly(1,3-propylene succinate)-terpoly(12-hydroxystearate); and a) an organic diisocyanate, (b) a chain extender, (c) acrosslinker, (d) a surfactant, (e) an optional foaming agent, (f) anoptional colorant, and (g) a catalyst.
 2. The polyurethane elastomer ofclaim 1 wherein the foaming agent is present, said colorant is presentand is comprised of a dye or a pigment, and wherein said organicdiisocyanate is selected from the group consisting of diphenylmethane4,4′-diisocyanate, isophorone diisocyanate, dicyclohexylmethane4,4-diisocyanate, hexamethylene 1,6-diisocyanate, naphthalene1,5-diisocyanate, and mixtures thereof.
 3. The polyurethane elastomer ofclaim 1 wherein said biobased polyester resin further comprisespoly(1,2-propylene-succinate), poly(1,2-propylene-sebacate),poly(1,3-propylene-succinate), poly(1,3-propylene-sebacate),poly(1,4-butylene-succinate), poly(1,4-butylene-sebacate),poly(1,2-propylene-azeleate), copoly(1,2-propylenesuccinate)-copoly(1,3-propylene succinate), copoly(1,2-propylenesebacate)-copoly(1,3-propylene sebacate), poly-12-hydroxy stearate,poly-ricinoleate, copoly(1,2-propylene succinate)-copoly(12-hydroxystearate), copoly(1,2-propylene-sebacate)-copoly(12-hydroxy stearate),copoly(1,3-propylene succinate)-copoly(12-hydroxy stearate),copoly(1,3-propylene sebacate)-copoly(12-hydroxy stearate),copoly(1,2-propylene succinate)-copoly(1,2-propylene sebacate),copoly(1,3-propylene succinate)-copoly(1,3-propylene sebacate),copoly(1,2-propylene succinate)-copoly(ricinoleate),copoly(1,2-propylene-sebacate)-copoly-(ricinoleate),copoly(1,3-propylene succinate)-copoly(ricinoleate),copoly(1,3-propylene sebacate) copoly(12-ricinoleate), orterpoly(1,2-propylenesuccinate)-terpoly(1,3-propylene-succinate)-terpoly(ricinoleate).
 4. Thepolyurethane elastomer of claim 1 wherein the hydrolytic stability isfrom about 80 to about 100 percent for tensile strength, and from about100 to about 150 percent for elongation.
 5. The polyurethane elastomerof claim 1 wherein said plasticizer further comprises a biobaseddi-methyl succinate, biobased bis(n-butyl) succinate, biobasedbis(propyl) succinate, biobased bis(2-butyl) succinate, biobasedbis(2-octyl) succinate, biobased bis(12-alkyl stearyl) succinate,biobased dimethyl sebacate, biobased diethyl sebacate or biobasedbis(ethyl) sebacate, biobased bis(n-butyl) sebacate, biobasedbis(propyl) sebacate, biobased bis(2-butyl) sebacate, biobasedbis(2-octyl) sebacate, biobased bis(12-alkyl stearylol) succinate,biobased bis(12-alkyl stearylol) sebacate, biobased bis(12-alkylricinoloyl) succinate, and biobased bis(12-alkyl ricinoloyl) sebacate,or mixtures thereof.